Carbon dioxide treatment of concrete upstream from product mold

ABSTRACT

Fresh concrete is treated with carbon dioxide prior to delivery to a product mold for forming concrete products. Carbon dioxide gas is directed through a manifold, which may be coupled to a feedbox or a hopper, upstream from the product mold. Treating the fresh concrete with the carbon dioxide gas while it is in a loose state prior to placement in the product mold may generally promote uniform and enhanced carbon dioxide uptake.

TECHNICAL FIELD

The present disclosure relates to methods of and apparatuses for makingconcrete products, for reducing the greenhouse gas emissions associatedwith making concrete products, and for sequestering carbon dioxide.

BACKGROUND

The following paragraphs are not an admission that anything discussed inthem is prior art or part of the knowledge of persons skilled in theart.

U.S. Pat. No. 4,117,060 (Murray) describes a method and apparatus forthe manufacture of products of concrete or like construction, in which amixture of calcareous cementitious binder substance, such as cement, anaggregate, a vinyl acetate-dibutyl maleate copolymer, and an amount ofwater sufficient to make a relatively dry mix is compressed into thedesired configuration in a mold, and with the mixture being exposed tocarbon dioxide gas in the mold, prior to the compression taking place,such that the carbon dioxide gas reacts with the ingredients to providea hardened product in an accelerated state of cure having excellentphysical properties.

U.S. Pat. No. 4,362,679 (Malinowski) describes a method of castingdifferent types of concrete products without the need of using a curingchamber or an autoclave subsequent to mixing. The concrete is casted andexternally and/or internally subjected to a vacuum treatment to have itde-watered and compacted. Then carbon-dioxide gas is supplied to themass while maintaining a sub- or under-pressure in a manner such thatthe gas diffuses into the capillaries formed in the concrete mass, toquickly harden the mass.

U.S. Pat. No. 5,935,317 (Soroushian et al.) describes a CO₂ pre-curingperiod used prior to accelerated (steam or high-pressure steam) curingof cement and concrete products in order to: prepare the products towithstand the high temperature and vapor pressure in the acceleratedcuring environment without microcracking and damage; and incorporate theadvantages of carbonation reactions in terms of dimensional stability,chemical stability, increased strength and hardness, and improvedabrasion resistance into cement and concrete products withoutsubstantially modifying the conventional procedures of acceleratedcuring.

U.S. Pat. No. 7,390,444 (Ramme et al.) describes a process forsequestering carbon dioxide from the flue gas emitted from a combustionchamber. In the process, a foam including a foaming agent and the fluegas is formed, and the foam is added to a mixture including acementitious material (e.g., fly ash) and water to form a foamedmixture. Thereafter, the foamed mixture is allowed to set, preferably toa controlled low-strength material having a compressive strength of 1200psi or less. The carbon dioxide in the flue gas and waste heat reactswith hydration products in the controlled low-strength material toincrease strength. In this process, the carbon dioxide is sequestered.The CLSM can be crushed or pelletized to form a lightweight aggregatewith properties similar to the naturally occurring mineral, pumice.

U.S. Pat. No. 8,114,367 (Riman et al.) describes a method ofsequestering a greenhouse gas, which comprises: (i) providing a solutioncarrying a first reagent that is capable of reacting with a greenhousegas; (ii) contacting the solution with a greenhouse gas under conditionsthat promote a reaction between the at least first reagent and thegreenhouse gas to produce at least a first reactant; (iii) providing aporous matrix having interstitial spaces and comprising at least asecond reactant; (iv) allowing a solution carrying the at least firstreactant to infiltrate at least a substantial portion of theinterstitial spaces of the porous matrix under conditions that promote areaction between the at least first reactant and the at least secondreactant to provide at least a first product; and (v) allowing the atleast first product to form and fill at least a portion of the interiorspaces of the porous matrix, thereby sequestering a greenhouse gas.

International Publication No. WO/2012/079173 (Niven et al.) describescarbon dioxide sequestration in concrete articles. Concrete articles,including blocks, substantially planar products (such as pavers) andhollow products (such as hollow pipes), are formed in a mold whilecarbon dioxide is injected into the concrete in the mold, throughperforations.

INTRODUCTION

The following paragraphs are intended to introduce the reader to themore detailed description that follows and not to define or limit theclaimed subject matter.

According to an aspect of the present disclosure, a method of formingconcrete products may include: supplying fresh concrete; treating thefresh concrete with carbon dioxide gas to form treated concrete; andsubsequent to the step of treating, delivering the treated concrete to aproduct mold adapted to form the concrete products.

According to an aspect of the present disclosure, an apparatus forforming concrete products may include: a product mold adapted to formthe concrete products; a component upstream of the product mold, andadapted to treat fresh concrete with carbon dioxide gas to form treatedconcrete, and deliver the treated concrete directly or indirectly to theproduct mold; and a gas delivery system connected to the component andadapted to control distribution of the carbon dioxide gas through thecomponent.

According to an aspect of the present disclosure, a process ofaccelerating the curing of concrete and sequestering carbon dioxide inthe concrete may include: supplying fresh concrete; directing aplurality of flows of carbon dioxide-containing gas under pressure intothe fresh concrete at a respective plurality of locations, to formtreated concrete; and subsequent to the step of directing, deliveringthe treated concrete to a product mold.

Other aspects and features of the teachings disclosed herein will becomeapparent, to those ordinarily skilled in the art, upon review of thefollowing description of the specific examples of the presentdisclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings included herewith are for illustrating various examples ofapparatuses and methods of the present disclosure and are not intendedto limit the scope of what is taught in any way. In the drawings:

FIG. 1 is a flow chart of a method of manufacturing concrete products;

FIGS. 2A to 2E are schematic views of an apparatus including a hopper, amodified feedbox, and a product mold;

FIGS. 3A and 3B are schematic views of an apparatus including a modifiedhopper, a feedbox, and a product mold;

FIGS. 4A and 4B are cutaway detail views of gas manifolds;

FIGS. 5A and 5B are cross section views of portions of the gas manifoldsof FIGS. 4A and 4B, respectively;

FIGS. 5C to 5E are cross section views of portions of other gasmanifolds;

FIG. 6 is a schematic diagram of a gas delivery system; and

FIG. 7 is a flow chart of a method of manufacturing concrete productswith carbon dioxide treatment.

DETAILED DESCRIPTION

Various apparatuses or methods are described below to provide an exampleof an embodiment of each claimed invention. No example described belowlimits any claimed invention and any claimed invention may coverapparatuses and methods that differ from those described below. Theclaimed inventions are not limited to apparatuses and methods having allof the features of any one apparatus or method described below or tofeatures common to multiple or all of the apparatuses or methodsdescribed below. It is possible that an apparatus or method describedbelow is not an embodiment of any claimed invention. Any inventiondisclosed in an apparatus or method described below that is not claimedin this document may be the subject matter of another protectiveinstrument, and the applicant(s), inventor(s) and/or owner(s) do notintend to abandon, disclaim or dedicate to the public any such inventionby its disclosure in this document.

Referring to FIG. 1, concrete products or concrete articles may be madecommercially by forming them in a molding machine and then curing theformed products. In a typical plant, various ingredients are conveyed toa mixer to make fresh concrete. The ingredients may be, for example,fine aggregate, coarse aggregate, fly ash, cement, chemical admixtures,and water. The mixed, fresh concrete is transferred to a hopper locatedabove a product mold.

In each production cycle, an appropriate quantity of concrete is passedfrom the hopper and into the product mold. The concrete may then beformed and compacted (shaken and compressed) in the product mold into aplurality of products, typically four or more. The products may leavethe molding machine on a tray, which is conveyed to a curing area. Theproducts may be cured slowly (7 to 30 days) by exposure to theatmosphere. However, in some commercial operations, the products may becured rapidly by steam or heat curing. For example, products may beplaced in a steam-curing chamber for 8 to 24 hours. The cured productsare removed from the curing area, and sent to further processingstations for packaging and transport to the end user.

Some production sequences make use of a feedbox. In each productioncycle, an appropriate quantity of concrete is passed from the hopper tothe feedbox, which is positioned above the product mold. The material inthe feedbox is passed into the product mold as part of a regular cycle.Once the product mold is filled and the product is formed, the cyclewill begin anew with new material being placed into the feed box. Anagitator grid may be positioned in the feedbox to agitate the concreteas it is dropped from the feedbox into the molding machine. The concreteis then formed and compacted in the product mold, as describedpreviously.

In some cases, the feedbox may be filled with dry cast concrete when thefeedbox is in a retracted position. The feedbox may then move from theretracted position to an extended position, in which it is arranged overan open top of the product mold. The dry cast concrete may then bedeposited from the feedbox into the product mold, by force of gravity.After depositing the dry cast concrete into the product mold, thefeedbox is moved from the extended position to the retracted position.The agitator grid may be positioned to impinge upon the concrete in thefeedbox, and assist the concrete in passing uniformly from the feedboxinto the product mold.

These processes may be adapted for use with a range of concrete productsthat are molded in batches, at an industrial scale, for example but notlimited to, blocks, pavers, other decorative or structural masonryunits, tiles or pipes, etc.

In a process of forming concrete blocks, for example, a pallet may bemoved by a conveyor system onto a pallet table or tray that, in turn,may be moved upwardly until the pallet contacts the product mold andforms a bottom for each of the one or more cavities of the product mold.Again, the feedbox, filled with dry cast concrete, may then be movedbetween the retracted and extended positions causing a feed drawer doorof the feedbox to open above a frame of the product mold. With help fromthe agitator grid, the concrete is dropped into the product mold, whereit fills the one or more cavities of the product mold via the open top.The product mold is filled optionally while being vibrated. The blockmolding machine may include a cutoff bar or blades, which may befixed-mounted to the feedbox, to scrape or wipe away excess dry castconcrete from the top of the one or more cavities as the feedbox isdriven back to the retracted position. The block molding machine mayfurther a stripper assembly having a compaction arm and at least onehead shoe, which may be moved into the one or more cavities of theproduct mold via their open tops to compress the dry cast concrete to adesired psi (pound-force per square inch) rating, while simultaneouslyvibrating the head shoe, product mold, pallet, and/or pallet table. Theform may be raised while the stripper assembly is still in its loweredposition leaving the shaped concrete blocks on the table. The compactionarm may then be raised, allowing the formed blocks to be ejected fromthe molding machine on the table. The cycle is then repeated while thetable of formed blocks travels on a conveyor to the steam chamber.

Generally, a production cycle for concrete blocks involves several stepsperformed in a very short period of time with the molding machine. Eachproduction cycle may make only a small number of blocks, for example 1to 16 or more, but lasts for only a very short period of time, forexample about 5 to 12 seconds. In this way, many blocks may be made in aworking shift and transferred to an accelerated curing chamber.

Accelerated curing is used to make the blocks stable relatively quickly,and thereby reduce the total production time until the blocks may beshipped as finished products. Accelerated curing typically involvesplacing the formed blocks in an enclosure or chamber, and controllingthe relative humidity and heat in the chamber for several hours. In coldclimates, steam may be used. When the ambient temperature is adequate,moisture may be added without additional heat. The blocks may sit in thecuring chamber for 8-48 hours before they are cured sufficiently forpackaging.

The block manufacturing process described above may be energy intensive.For example, energy required for the steam curing may exceed 300 MJ pertonne of blocks. Depending on the source of this energy, the greenhousegas emissions associated with steam curing may be significant, up toabout 10 kg of CO₂ per tonne of block. Also, while most blocks may bewell formed, in a typical production shift several blocks may be damagedas they are stripped from the form and have to be discarded.

In general, the concepts described herein pertain to methods of andapparatuses for forming concrete products, in which fresh concrete istreated with carbon dioxide gas to form treated concrete. The treatedconcrete is subsequently delivered to a product mold to form theconcrete products.

Treating the concrete to carbon dioxide gas while it is in a loose stateprior to placement in the product mold may generally promote uniform andenhanced carbon dioxide uptake. Despite a short relatively exposuretime, the inventors have recognized that the carbon dioxide uptake maybe a significant portion of the theoretical maximum uptake, which forconventional cement may be approximately half of the mass of the cementin the mixture. Furthermore, the resulting calcium carbonate may be welldistributed through the concrete, which may thereby improve the materialproperties of the formed concrete product.

As described in further detail herein, the carbon dioxide gas may bedelivered at least in part while the concrete is being portioned forplacement into the product mold. The carbon dioxide gas may be directedat the concrete for a period of time of about 60 seconds or less. Thecarbon dioxide gas may be delivered at an applied pressure of about 875kPa above atmospheric pressure, or less. The gas may be delivered at arate of about 80 litres per minute per litre of the concrete, or less.The delivered gas may be carbon dioxide-rich, e.g., at least about 90%carbon dioxide, and may be derived from a pressurized gas source. Thegas may be heated. The gas may include a flue gas, which may be derivedfrom a steam or heat curing process for products formed by the moldingmachine.

The addition of carbon dioxide may promote an alternate set of chemicalreactions in the concrete resulting in different reaction products. Inparticular, thermodynamically stable calcium carbonate (limestone)solids may be formed preferentially to calcium hydroxide (portlandite)products. The carbon dioxide may be solvated, hydrated and ionized inwater in the concrete to produce carbonate ions. These ions may combinewith calcium ions from the cement to precipitate calcium carbonate inaddition to amorphous calcium silicates. In this way, carbon dioxide maybe sequestered in the concrete blocks as a solid mineral. Excess gas, ifany, may be vented away from the treated concrete mass. Otherwise, theproduction cycle of a given concrete product may remain generallyunchanged.

The carbonated mineral reaction products may increase the early strengthof the concrete. This may allow accelerated curing to be eliminated, ora reduction in time or temperature, or both. The energy consumption ortotal time, or both, of the concrete product making process may therebybe reduced. If steam curing would otherwise be used, then, depending onhow the energy for steam curing is generated, there may be a furtherreduction in the greenhouse gas emissions associated with making theconcrete products. The carbonated products may also exhibit one or moreof decreased permeability or water absorption, higher durability,improved early strength, reduced efflorescence, and reduced in serviceshrinkage. The number of products that are damaged when they arestripped from the mold, conveyed or otherwise processed prior topackaging may also be reduced.

The present teachings may be adapted for use with a range of concreteproducts that are molded in batches, at an industrial scale, for examplebut not limited to, blocks, pavers, other decorative or structuralmasonry units, tiles or pipes, etc.

Referring now to FIG. 2A, an apparatus 10 for forming concrete productsis illustrated to include a conveyor 12, a hopper 14, a modified feedbox16 and a product mold 18. The conveyor 12 supplies fresh concrete 20 toan inlet 22 of the hopper 14, either continuously or intermittently. Anoutlet 24 of the hopper 14 in a closed position maintains the concrete20 residing in the hopper 14. Referring to FIG. 2B, the outlet 24 of thehopper 14 is moved to an opened position to supply the concrete 20 tothe feedbox 16. The feedbox 16 is shown in a retracted position, andincludes an agitator grid 30.

In the example illustrated, the feedbox 16 includes a first gas manifold26. The first gas manifold 26 is positioned to direct a carbon dioxidegas flow 28 at the concrete 20 residing within the feedbox 16. The firstgas manifold 26 is shown mounted to an inner surface of a peripheralwall of the feedbox 16. In other examples, the gas manifold may beformed as part of the agitator grid 30. Also, as shown, the carbondioxide gas flow 28 may be directed by the first gas manifold 26 towardsthe concrete 20 to impinge an upper surface of the concrete 20.Alternatively, or additionally, the first gas manifold 26 may bepositioned so that the carbon dioxide gas flow 28 is injected by thefirst gas manifold 26 directly into the volume of the concrete 20.

Delivery of carbon dioxide by the first gas manifold 26 may be generallysynchronized with the inlet 22 of the hopper 14. For example, thepressurized flow 28 may be provided either once the inlet 22 is openedand the concrete 20 is accumulating in the feedbox 16, or, optionally,the flow 28 may begin immediately prior to opening the inlet 22.

Referring to FIG. 2C, the outlet 24 of the hopper 14 is moved to theclosed position to maintain the concrete 20 in the hopper 14. Thefeedbox 16 is moving towards an extended position, from overtop a baseplate 32 to above the product mold 18. A second gas manifold 34 ispositioned to direct a carbon dioxide gas flow 36 at a stream of theconcrete moving between the feedbox 16 and the product mold 18.Referring to FIG. 2D, the feedbox 16 continues to move towards anextended position, as treated concrete 20 a is being delivered to theproduct mold 18. Finally, referring to FIG. 2E, the feedbox 16 is shownin the extended position, and all of the treated concrete 20 a is showndelivered into the product mold 18.

Delivery of carbon dioxide by the second gas manifold 34 may begenerally synchronized with movement of the feedbox 16 between theretracted and extended positions. For example, the pressurized flow 36may be provided either once the feedbox 16 has begun to move over theproduct mold 18 and the concrete 20 is accumulating in the product mold18, or, optionally, the flow 36 may begin immediately prior to thiswhile the feedbox 16 remains positioned above the base plate 32.

In the example illustrated in FIGS. 2A to 2E, it should be appreciatedthat the gas manifolds 26, 34 may be installed as a retrofit to anexisting feedbox and product mold configuration.

Referring now to FIG. 3A, an apparatus 10 a for forming concreteproducts is illustrated to include the conveyor 12, a modified hopper 14a, a feedbox 16 a and the product mold 18. The conveyor 12 suppliesfresh concrete 20 to an inlet 22 a of the hopper 14 a, eithercontinuously or intermittently. An outlet 24 a of the hopper 14 a isshown in an open position to supply the concrete 20 to the feedbox 16 a.In the example illustrated, the hopper 14 a includes at least one thirdgas manifold 38. The third gas manifold 38 is shown mounted to an innersurface of a peripheral wall of the hopper 14 a, and is positioned todirect at least one flow of carbon dioxide gas at the concrete 20residing within the hopper 14 a.

Referring now to FIG. 3B, an apparatus 10 b for forming concreteproducts is illustrated to include the conveyor 12, a modified hopper 14b, a feedbox 16 b and the product mold 18. The conveyor 12 suppliesfresh concrete 20 to an inlet 22 b of the hopper 14 b. An outlet 24 b ofthe hopper 14 b is shown in an open position to supply the concrete 20to the feedbox 16 b. In the example illustrated, the hopper 14 bincludes at least one fourth gas manifold 40. The fourth gas manifold 40is shown mounted to an outer surface of the peripheral wall of thehopper 14 a, and is positioned to direct at least one flow of carbondioxide gas at a stream of the concrete 20 moving out of the outlet 24 bof the hopper 14 b, and into the feedbox 16 a.

In the examples illustrated in FIGS. 3A and 3B, the gas manifolds 38, 40may be shaped to correspond to the shape of the respective peripheralwall of the hopper 14 a, 14 b. For example, the gas manifolds 38, 40 maygenerally square or ring shaped, so as to extend circumferentially aboutthe concrete 20. Furthermore, it should be appreciated that the gasmanifolds 38, 40 may be installed as a retrofit to an existing hopper,and may be designed to operate in synchronization with the opening andclosing of the respective outlet 24 a, 24 b.

Referring to FIG. 4A, the first gas manifold 26 is shown to includefinger elements 42 and a supporting spine 44. In the exampleillustrated, each of the finger elements 42 is positioned generallyperpendicular relative to the spine 44, and each includes an inward endadjacent to the spine 44, and an outward end spaced apart from the spine44. The finger elements 42 may be spaced apart at regular intervalsacross the spine 44, or may be positioned strategically depending on adesired gas flow profile across the spine 44. In some examples, thespine 44 may be generally elongate, and have a length and shape that isappropriate for the mounting location. However, in other examples, thespine may be arc-shaped. The finger elements 42 may have differentlengths and different diameters depending on the desired gas flowrequirements. The spine 44 is shown affixed to a mounting structure 46that allows the first gas manifold 26 to be securely mounted.

In the example illustrated, the finger elements 42 and the spine 44 arehollow. Internal gas passages 48 in the finger elements 42 may runthrough the entirety of the finger elements 42 and terminate in aperforation or aperture 50. The apertures 50 are distributed across thespine 44 for delivering flows of carbon dioxide gas. The configurationof the finger element 42, the spine 44 and the aperture 50 is also shownin FIG. 5A.

With continued reference to FIG. 4A, the apertures 50 may be located atthe outward ends of the finger elements 42. The number and size offinger elements 42, and/or the number and size of the apertures 50, maybe selected to generally balance a desire to direct carbon dioxide gasacross the entirety of the concrete at the location of the gas manifold26, and a desire to provide some back pressure to gas flow to helpequalize the gas flow rate through the apertures 50 in differentlocations. Furthermore, the size of the apertures 50 may vary, e.g.,having a diameter of between 1 mm and 10 mm. The size and number of theaperture 50 may be kept small enough so that a gas flow rate througheach of the aperture 50 may be sufficient to push carbon dioxide gasinto the concrete mass, if in contact with the concrete, so as toprevent or at least deter liquids or suspensions in the concrete frominfiltrating the aperture 50.

A gas passage 52 in the spine 44 may run axially from one end to theopposite end, in fluid communication with each of the gas passages 48and extending beyond the outermost finger elements 42. At one end of thespine 44, there is an gas inlet fitting 54 for connection to a gas feedconduit (not shown), and which is in fluid communication with the gaspassage 52. The size of the gas passage 48 along the length of the spine44 may vary depending on the relative distance from the gas inletfitting 54 in order to promote equal gas flow rates into each of thefinger elements 42.

Connections between the finger elements 42 and the spine 44 may bewelded or threaded. A threaded connection may allow the finger elements42 to be changed depending on the application. The connection may alsobe a quick connect setup, allowing the finger elements 42 to take theform of a tube, such as rigid or flexible plastic tubing.

Referring now to FIG. 4B, according to another example, the first gasmanifold 26 a is shown to include a supporting spine 44 a, and withoutfinger elements. Apertures 50 a are distributed across the spine 44 afor delivering flows of carbon dioxide gas. A gas passage 52 a in thespine 44 a may run axially from one end to the opposite end, in fluidcommunication with each of the apertures 50 a. The configuration of thespine 44 a and the apertures 50 a is also shown in FIG. 5B.

FIGS. 5C, 5D and 5E show additional exemplary configurations. In FIG.5C, the aperture 50 b is shown to be generally aligned with an axis ofthe finger element 42 b, and has a different, smaller cross sectionalarea. Furthermore, apertures may additionally or alternatively bepositioned not just on the outward end of the finger element, but on thesides of the finger elements, on sections that may be expected to be incontact with concrete. For example, in FIG. 5D, the aperture 50 c isshown to be generally perpendicular to an axis of the finger element 42c. FIG. 5E shows apertures 50 d that are arranged at an angle relativeto an axis of the finger element 42 d.

It should be appreciated that the configurations of the gas manifolds26, 26 a shown in FIGS. 4A and 4B, respectively, may also be implementedas the gas manifolds 34, 38, 40 described herein. In any case, the gasmanifold is arranged so that the apertures are either in contact withthe concrete to be treated, or otherwise in relatively close proximity.

Referring now to FIG. 6, a gas delivery system 56 is adapted to controldistribution of carbon dioxide gas through at least one component of amolding machine, upstream of the product mold. In some examples, the gasdelivery system 56 may be implemented as a retrofit to an existingmolding machine, so that no parts of the molding machine may need to bechanged or significantly modified. In these examples, the gas deliverysystem 56 may be provided as additional components to the moldingmachine, which once installed do not interfere with the motion of anymoving parts of the molding machine.

The gas delivery system 56 is shown to include at least one of the gasmanifolds 26, to provide carbon dioxide gas to the feedbox 16 (FIG. 2B).Additionally, or alternatively, the gas delivery system 56 may includeat least one of the gas manifolds 34, 38, 40 to provide carbon dioxidegas to the feedbox 16 or the hopper 14 (FIGS. 2C, 3A and 3B).

The gas inlet fitting 54 of the gas manifold 26 is connected by a gasfeed line or conduit 58 to at least one gas supply valve 60. The conduit58 may be sufficiently flexible to allow for movement of the gasmanifold 26 and normal agitation during the production cycle. On theother hand, the conduit 58 may be sufficiently rigid, or tied-off, orboth, to ensure that it does not interfere with any moving part of themolding machine (identified by reference numeral 66). The gas supplyvalve 60 governs flow of pressurized gas between a pressurized gassupply 62 and the gas manifold 26. In some examples, the gas supplyvalve 60 may include several gate valves that permit the incorporationof calibration equipment, e.g., one or more mass flow meters.

When the gas supply valve 60 is open, pressurized carbon dioxide-richgas flows from the gas supply 62 to the gas inlet fitting 54, throughthe gas passages 52, 48 and out through the apertures 50. The gas supply62 may include, for example, a pressurized tank (not shown) filled withcarbon dioxide-rich gas, and a pressure regulator (not shown). The tankmay be re-filled when near empty, or kept filled by a compressor (notshown). The regulator may reduce the pressure in the tank to a maximumfeed pressure. The maximum feed pressure may be above atmospheric, butbelow supercritical gas flow pressure. The feed pressure may be, forexample, in a range from 120 to 875 kPa. A pressure relief valve (notshown) may be added to protect the carbon dioxide gas supply systemcomponents. The carbon dioxide gas supplied by the gas supply 62 may beat about room temperature. However, if not, a heater (not shown) may beadded to bring the uncompressed gas up to roughly room temperaturebefore flowing to the gas manifold 26.

The gas supply valve 60 may be controlled by a controller 64. Thecontroller 64 may be, for example, an electronic circuit or aprogrammable logic controller. In general, the controller 64 manages gasflow through the gas supply valve 60. The controller 64 may be connectedto the molding machine 66 such that the controller 64 may sense when themolding machine 66 has begun or stopped a stage of operation, andthereby synchronize delivery of the carbon dioxide gas with theproduction cycle of the molding machine 66. For example, the controller64 may be wired into an electrical controller or circuit of the moldingmachine 66 such that during one or more stages of operation a voltage,current or another signal is provided to the controller 64.Alternatively or additionally, one or more sensors may be added to themolding machine 66, adapted to advise the controller 64 of conditions ofthe molding machine 66. When not retrofitted to an existing moldingmachine, functions of the controller 64 may be integrated into a controlsystem of the molding machine. Further alternatively, the controller 64may consider a timer, a temperature sensor, a mass flow, flow rate orpressure meter in the conduit 58, or other devices, in determining whento stop and start gas flow (e.g., a solenoid). In general, thecontroller 64 is adapted to open the gas supply valve 60 at a timebeginning between when the concrete passes in the vicinity of theapertures 50, and close the gas supply valve 60 after a desired amountof carbon dioxide gas has been delivered over a desired period of time.

Mass of carbon dioxide gas sent to the gas manifold 26 may be controlledusing a mass flow controller 68 that is arranged between the gas supply62 and the gas supply valve 60. The mass flow controller 68 maycommunicate with the controller 64, once the gas supply 62 has delivereda suitable amount of gas to the gas manifold 26. The controller 64 maythen close the gas supply valve 60, and thereby cease supply of thecarbon dioxide gas through the gas manifold 26.

In some examples, the controller 64 may connect to a plurality of thegas manifolds 26, arranged to distribute the gas to various specificlocations of the molding machine, including different portions of thefeedbox and/or the hopper, as described herein. In such examples, thecontroller 64 may generally synchronize gas delivery at the variouslocations with the relevant steps of the given production cycle. Theconcrete may pass through the molding machine in a way in which somelocations will be in contact with concrete sooner, or in greaterquantities than other locations. Accordingly, the controller 64 maycontrol distribution of the gas to the various locations at differenttimes and different quantities.

The gas for treating the concrete may have a high concentration ofcarbon dioxide, and minimal concentrations of any gases or particulatesthat would be detrimental to the concrete curing process or to theproperties of the cured concrete. The gas may be a commercially suppliedhigh purity carbon dioxide. In this case, the commercial gas may besourced from a supplier that processes spent flue gasses or other wastecarbon dioxide so that sequestering the carbon dioxide in the gassequesters carbon dioxide that would otherwise be a greenhouse gasemission.

Other gases that are not detrimental to the curing process or concreteproduct may be included in a treatment gas mixture. However, if the gasincludes other gases besides carbon dioxide, then the required flow rateand pressure may be determined based on the carbon dioxide portion ofthe gas alone. The total flow rate and pressure may need to remain belowa level that prevents the formation of bubbles or sprays concretematerials out of the feedbox, which may limit the allowable portion ofnon-carbon dioxide gases. In some cases, on site or nearby as-capturedflue gas may be used to supply some or all of the gas containing carbondioxide, although some particulate filtering or gas separation may berequired or desirable.

In general, in accordance with the teachings of the present disclosure,carbon dioxide gas is delivered by a gas delivery system to a supply ofconcrete upstream from molding. Referring now to FIG. 7, a method 100begins by inserting a tray into a molding machine in step 102. In step104, a product mold is placed on the tray. In step 106, an outlet of ahopper is opened to deliver fresh concrete to a feedbox. In step 108,which may be concurrent with step 106, a gas supply valve of the gasdelivery system is opened to start delivering carbon dioxide gas intothe feedbox. In step 110, the feedbox has been filled with theappropriate amount of concrete. In step 112, the hopper stops providingconcrete to the feedbox. In step 114, the concrete in the feedbox isdelivered into the product mold. In step 116, the gas valve of the gasdelivery system is closed to cease delivery of gas to the feedbox. Instep 118, the treated concrete in the product mold is compacted andconsolidated. In step 120, the product mold is stripped by raising theproduct mold and then the compaction arm. Thereafter the tray with atleast one molded concrete product is removed for further processing,such as further curing, if any, packaging and distribution. The strippedproducts may continue to a steam or heat curing process; however, thetime or temperature of the curing required to produce a desired strengthmay be reduced. For example, the concrete products may be cured at atemperature between 35 and 70° C. and relative humidity of about 75% ormore. Optionally, flue gas from the steam or heat curing may berecaptured and injected into other blocks.

The exact order of the steps 104, 106, 108, 110, 112, 114, 116, 118 and120 may be varied, but, in some examples, carbon dioxide may be directedat the concrete at least during step 114 while the concrete is in thefeedbox (or hopper). The inventors believe that aligning the delivery ofthe carbon dioxide gas with the movement of the concrete as it passesthrough the feedbox (or hopper) may facilitate an even distribution andmixing of the carbon dioxide within the concrete. With a relativelyrapid delivery, for example, delivering carbon dioxide gas for 10seconds or less, the treatment method may only minimally slow themolding operation, if at all. This rapid delivery may serve todistribute the carbon dioxide throughout the concrete mix before theproduct formation to maximize the exposure of the concrete mix to carbondioxide, and the calcium carbonate forming reactions may not inhibit thesubsequent compaction and formation of the concrete products.

If the delivered gas contains essentially only carbon dioxide or othernon-polluting gases or particulates not detrimental to health, then anyexcess gas not absorbed by the concrete may be allowed to enter theatmosphere. Provided that the total amount of carbon dioxide per cycledoes not exceed the maximum possible carbon uptake, very little carbondioxide will be emitted. However, particularly if un-separated flue gasis used to supply the carbon dioxide, other gasses may be emitted. Gasesleaving the mold may be collected by a suction pressure ventilationsystem, such as a fume hood or chamber, for health and safety orpollution abatement considerations.

In accordance with the teachings of the present disclosure, concretesamples were produced in a lab and subjected to bench scale carbonationas part of their formation.

The standard concrete was analogous to a conventional concrete block mixdesign. It contained 1.494 kg of cement, the equivalent of 12.65 kg ofsaturated surface dry fine aggregate (Milford sand) and the equivalentof 5.90 kg of saturated surface dry fine aggregate (Folly Lake ⅜″stone). 2.6 ml of a superplasticizer was used. Water was added to themix to achieve a dry mix concrete with a water to cement ratio of about0.74. The batch size of 20 kg was sufficient to create 5 standardconcrete cylinders with dimensions of 100 mm diameter and 200 mm height.

The concrete was mixed for two minutes in a Hobart 30 quart mixer. Theconcrete was portioned into 3.75 kg charges. The charges of concretewere emptied into a cylinder mold subjected to vibration on a vibratingtable. A pneumatic ram was used to finish the production by pushing thematerial into the mold with a force of 800 lbs. The compaction occurredin conjunction with the vibration, as per dry cast production of aconcrete block.

Samples were demolded at 24 hours and submerged in a room temperaturebath of water saturated with hydrated lime until the time of compressiontesting.

Carbonated samples were produced with a slightly wetter concrete mixwith a water to cement ratio of about 0.77. It was observed that thecarbonation treatment may promote a slight reduction in the effectivewater content of a sample. As compensation, slightly more water wasadded to the mix for carbonated concrete.

The carbon dioxide gas was introduced through a ring secured to the topof the mold. When the concrete charge was emptied into the mold theconcrete would pass through the ring. The ring had hollow walls with arow of apertures regularly spaced on the inner surface. A gas connectionallow for a gas stream to be injected into the ring and flow through theapertures to the interior space of the ring. The concrete would passthrough the carbon dioxide stream immediately prior to coming to rest inthe mold. The gas delivery was manually controlled to be aligned withthe emptying of the concrete charge into the mold. The typical time ofcarbon dioxide delivery was 6 to 8 seconds. The gas was a conventional,unblended, substantially pure carbon dioxide, readily available from anindustrial gas supplier in compressed cylinders.

Table 1 shows the results of 7 day compressive strength testing oncontrol specimens. The set of 15 specimens consisted of 3 batches of 5specimens. The column labeled “Sample” gives an arbitrary number to eachof the 15 specimens. The first batch is samples 1 to 5, the second batchis samples 6 to 10 and the third batch is samples 11 to 15. Theconcretes were oven dried to check the moisture. A fresh sample of eachbatch was immediately placed into an oven at 120° C. and held until themass constant. The difference in the initial sample mass and finalsample mass was adjusted to compensate for the absorption of theaggregates and expressed as a percentage of the dry mass. The threecontrol batches had water contents of 4.99%, 6.38% and 5.37%. Thecollected data has a mean of 9.44 MPa and a standard deviation of 1.23MPa.

TABLE 1 7 day strength of dry mix control concrete produced in a lab.Sample Compressive Strength (MPa) 1 11.75 2 10.65 3 10.34 4 9.56 5 11.756 8.68 7 9.38 8 8.04 9 9.76 10 8.19 11 8.51 12 8.08 13 9.12 14 9.49 158.33

Table 2 shows the results of 7 day compressive strength testing oncarbonated specimens. The carbonated samples were subject to a 2.9 LPMflow of carbon dioxide gas as the material was placed into the mold. Theset of 15 specimens consisted of 3 batches of 5 specimens. The columnlabeled “Sample” gives an arbitrary number to each of the 15 specimens.The first batch is samples 1 to 5, the second batch is samples 6 to 10and the third batch is samples 11 to 15. The concretes were oven driedto check the moisture. A fresh sample of each batch was immediatelyplaced into an oven at 120° C. and held until the mass constant. Thedifference in the initial sample mass and final sample mass was adjustedto compensate for the absorption of the aggregates and expressed as apercentage of the dry mass. The three control batches had water contentsof 6.25%, 6.23% and 6.17%. The collected data has a mean of 10.95 MPaand a standard deviation of 1.35 MPa.

TABLE 2 7 day strength of carbonated dry mix concrete produced in a lab.Sample Compressive Strength (MPa) 1 10.47 2 9.64 3 10.90 4 10.22 5 8.556 10.98 7 10.07 8 11.37 9 10.64 10 13.00 11 14.04 12 11.27 13 11.04 149.93 15 12.07

Strength was not found to be a function of water content in the range ofwater contents observed and in regards to the mix design and productiontechnique used. Thus, the results suggest that the carbonation treatmentimproved the strength of the concrete. Statistical analysis of anindependent two-sample t-test, using equal sample sizes, and assumingequal underlying variance suggests that the carbonated concrete isconclusively stronger than the control concrete with a 95% confidence(according to a calculated test statistic of 3.187 compared to thecritical minimum test statistic at 95% confidence and 28 degrees offreedom of 2.00).

While the above description provides examples of one or more apparatusesor methods, it will be appreciated that other apparatuses or methods maybe within the scope of the accompanying claims.

1-21. (canceled)
 22. A method of retrofitting an existing apparatus forforming concrete products, wherein the apparatus comprises a componentlocated upstream of a product mold and adapted to deliver concrete tothe product mold, comprising adapting the component to treat freshconcrete to be delivered to the product mold by the component withcarbon dioxide gas to form treated concrete, wherein the step ofadapting comprises adding to the existing component a gas deliverysystem that is configured to direct the carbon dioxide gas onto asurface of the fresh concrete or at a stream of the fresh concrete, orany combination thereof, and wherein the gas delivery system is providedwith one or more gas manifolds comprising a plurality of apertures,wherein the apertures are positioned to be in close proximity to theconcrete but not in contact with the concrete, thereby retrofitting theexisting apparatus into a retrofitted apparatus.
 23. The method of claim22, wherein the component comprises a hopper, a feedbox, or acombination thereof. 24-25. (canceled)
 26. The method of claim 22,wherein the product mold is adapted to form a product selected from thegroup consisting of blocks, pavers, decorative masonry units, tiles, andpipes.
 27. (canceled)
 28. The method of claim 22, wherein, in the stepof adapting, the one or more gas manifolds comprising a plurality ofapertures are mounted to an inner surface of a peripheral wall of thecomponent, mounted to an outer surface of a peripheral wall of thecomponent, formed as part of a subcomponent of the component or acombination thereof.
 29. The method of claim 23, wherein theretrofitting further comprises adding to the existing apparatus one ormore sensors and a controller for synchronizing the delivery of thecarbon dioxide gas with an action of the component, an action of asubcomponent of the component, a step of a production cycle, or anycombination thereof.
 30. The method of claim 29, wherein the controlleris in electronic communication with a control circuit of the existingapparatus and/or one or more sensors or devices added to the existingapparatus, and wherein the controller is further in communication withone or more gas manifolds for supplying the carbon dioxide gas to thefresh concrete.
 31. The method of claim 29, wherein the sensors and thecontroller are adapted to align the timing of delivery of carbon dioxidegas with movement of the fresh concrete as it passes through the feedboxand/or the hopper.
 32. The method of claim 29, wherein the controller isadapted to open a gas supply valve for supplying the carbon dioxide gaswhen the fresh concrete passes in the vicinity of an aperture of a gasmanifold comprising a plurality of apertures for delivering the carbondioxide gas onto the surface and/or at the stream of the fresh concrete,and close after a desired amount of the carbon dioxide gas has beendelivered over a desired amount of time.
 33. The method of claim 32,wherein the desired amount of time is 60 seconds or less. 34-35.(canceled)
 36. The method of claim 35, wherein the diameter of theapertures is between 1 mm and 10 mm.
 37. The method of claim 28 claim 22wherein the component is a feedbox.
 38. The method of claim 28 whereinthe component is a hopper.
 39. The method of claim 22, wherein the gasdelivery system comprises a carbon dioxide feed tank and a pressureregulator.
 40. The method of claim 39, wherein the pressure regulatormaintains a maximum feed pressure for the carbon dioxide gas aboveatmospheric pressure but below supercritical pressure.
 41. The method ofclaim 40, wherein the pressure regulator maintains a feed pressure inthe range from 120 kPa to 875 kPa.